Textile finishing composition, application process, and resulting product



United States Patent Office 3,lfi8, il5 Patented Feb. 2, 1965 3,168,415 TEXTILE FINESHTNG COMPOSITIGN, APPLICA- TION PRUCESS, AND RESULTENG PRODUCT Herman B. Goldstein, Raymond J. Pelticr, and Michael A.

Silvestri, Cranston, 11.1., assignors to Sun Chemical Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 4, 1963, Ser. No. 270,553 17 Claims. (Cl. 117-1394) This invention relates to the treatment of textile materials and in particular to the treatment of textile materials with alkylol derivatives of nitrogen containing compounds. I

The formation of durable finishes on fabrics has been an object of many investigations. These durable finishes should be permanent as well as capable of rendering the fabric resistant to water, wrinkling, and shrinking. Furthermore, these finishes must be capable of being applied without detrimental changes in other fabric properties such as tensile strength, crispness, and abrasion resistance.

Heretofore, fabrics, especially cellulose fabrics, have been treated with resinous materials such as urea-formaldehyde resins, u-rea-thiourea-formaldehyde resinous reaction products and the like to improve their resistance to wrinkling and creasing. However, fabrics treated with these resinous materials pick up chlorine during bleaching operations which employ chlorine such as that encountered in the form of a hypochlorite. On ironing severe discoloration is encountered and generally a loss in tensile and/ or tear strengths results in fabrics that have been bleached in this manner. In those cases where severe discoloration is encountered, the treatment with these products is unsuitable when a white fabric is ultimately desired. In some cases as much as 80 percent loss in strength is encountered as a result of the action of heat as in ironing, on fabrics treated with these resinous products and bleached with chlorine.

Heretofore, fabrics have been treated with methylol derivatives of organic amides, formed from the reaction of formaldehyde with amides such as urea, melamine and dicarboxylic acid diamides. Fabrics thus treated are often susceptible to discoloration and strength loss after hypochlorite bleaching. To prevent this, fabrics have been treated with compounds having alkyl substituents on the amido nitrogen. These substituents replace any amido hydrogen remaining after the reaction with formaldehyde and thereby remove the groups that react with hypochlorites. However, all of these suffer some disadvantages, for example they have reduced effectiveness in producing desired wrinkle resistance and lack durability to such acidic conditions as souring which is encountered in most commercial laundries.

It is therefore an object of this invention to produce compounds of the organic amide class having improved properties.

Another object of this invention is to provide novel coating compositions which will provide novel finishes for fabrics.

Still another object of this invention is to provide novel organic amide compounds which can be used to impart durable wrinkle resistance finishes to fabrics.

A still further object of this invention is to provide novel organic amide compositions which will impart chlorine resistance finishes to fabrics.

It is still another object of this invention to provide novel fabric coating compositions which will be durable to laundering in which acidic or alkaline conditions are encountered.

In accordance with the present invention it has been found that novel compounds comprising alkylol derivatives of tris(carbamoyl alkyl) amines will impart improved crease and chlorine resistance to fabrics treated therewith. These novel compounds can be illustrated by the following formula:

CH CHgNUJH OIDB l N-CHzCHzfllIHCHgOHM i CH CHgfIN(CHzOH)n wherein n is an integer of 1 or 2 and the sum of all ns is equal to 4 to 6 inclusive. For brevity, compounds of the above composition will be referred to as: tris(N-methylol carbamoylethyl) amine.

The alkylol derivatives of the tris-carbamoyl amines may be prepared by reacting at least four (4) mols of an alkylolating agent, e.g., a lower aliphatic aldehyde, especially, formaldehyde or formaldehyde donating compounds with a mol of a tris amine compound especially tris(carbamoylethyl) amine for from 1 to 24 hours at an alkaline pH, preferably 7.0 to 9.0 or higher, in the presence of a solvent.

Tris(carbamoylethyl) amine may be prepared in accordance with the methods and procedures described in U.S. 2,663,733 to Lee A. Subluskey, dated December 22, 1953, wherein an aqueous solution of acrylamide is reacted with ammonia in suitable proportions. The tris- (carbamoylethyDamine product may then be recovered by crystallization from the concentrated solution.

Tris(carbarnoylethyl)amine may also be prepared in accordance with the methods and procedures set forth in US. 2,5 80,832 to Edward W. Pietrucza, dated January 1, 1952, wherein acrylic acid esters and aqueous ammonia are reacted in a liquid reaction medium containing a hydroxylated solvent. The tris(carbarnoylethyl)amine product is then recovered from the reaction mixture.

Likewise, tris(carbamoylethyl)amine may also be pre- 4 pared by reacting acrylonitrile with water in the presence of sulfuric acid. The resulting acrylamide sulfuric acid solution is neutralized with an excess of ammonia resulting in the formation of a tris(carbamoylethyl)amine which can be recovered therefrom. The reaction of a tris amine compound, especially tris- (carbamoylethyl)amine, with formaldehyde or a formaldehyde donating substance may be carried out in a temperature range of from about 10 C. to about 80 C., preferably in a temperature range of from about 20 C. to about 50 C. The reaction should be carried out in the presence of a solvent. Suitable solvents which may be employed are, for example, water and lower aliphatic alcohols such as methanol, ethanol, propanol and aqueous mixtures thereof. The reaction time, which may vary from 2 to 24 hours, is dependent on the temperature of the reaction media, that is, the lower the reaction temperature, the longer the reaction time. For best results the reaction should be carried out at a temperature of about 50 C. for a period of about 4 hours. The ratio of tris amine compound to formaldehyde is critical. Therefore, it is essential that at least 4.0 mols of formaldehyde be employed for each mol of tris amine. It is preferred that the formaldehyde be in a ratio of from about 4.0 to 6.0 mols and more preferably in a range of from about 4.5 to 6.0 mols per mol of tris amine.

Fabrics may be treated with a solution containing tris (N-methylol carbamoylethyl) amine to render them chlo- 7 3 rim: and crease resistant. The tris(N-methylol carbamoylethyl) amine is diluted with an aqueous solvent to form a padding bath concentration of from about 2 to 30 percent solids by weight and more preferably about 10 percent solids by weight. About 5.0 to about 30.0 percent by weight of a catalyst, based on the weight of the tris (N- methylol carbamoylethyl) amine present, is added to the padding bath. The pH of the bath may then be adjusted to a range of from about 3 to about 5 by the addition of sufficient acid it the catalyst used does not produce this pH range. The padding bath, comprising an alkylol amide and catalyst, prepared as described above is padded on to a cloth by dipping and then passing the impregnated cloth through eflicient squeeze rolls to give a 70 to 80 percent wet pickup. The wet fabric is dried at a temperature of from 100 to 150 C., and then further heated for from 1 to 5 minutes at a temperature of from 150 to 180 C. to facilitate curing. The curing step is followed by an alkaline afterwash in warm detergent solution to remove any excess unreacted crease resistance agent and then dried.

Materials which have been found useful as catalysts are various acidic compounds, latent acid compounds or metallic salts. For example, the hydrochloride of 2- amine-2-methyl-l-propanol, maleic acid, tartaric acid, citric acid, zinc nitrate, magnesium chloride, etc. may be used. Magnesium chloride has been found to be unusually effective and is ordinarily preferred as the catalyst.

It has further been unexpectedly found that the tensile strength of fabric may be enhanced by the addition of a dimethylol triazone to the padding bath. Triazones which are within the contemplation of this invention may desirably be prepared by reacting urea, formaldehyde and a primary amine together in suitable proportions in mildly alkaline solutions. The triazones may also be prepared by the reaction of ethylene diamine with urea and formaldehyde at a temperature from 80 to 85 C. This mixture is then reacted with formaldehyde to form a meth ylol derivative of a triazone compound.

The triazone compounds may be prepared by first reacting urea and formaldehyde together and then adding a primary amine, or all three ingredients may be added simultaneously.

The triazone compounds may thus be prepared using primary monoamines and particularly a member of the class of primary monoamines consisting of the lower alkyl monoamines, such as methylamine, ethylamine, propylamine, isopropylamine, n-butylamine and n-hexylamine; the lower hydroxyalkyl monoamines such as ethanolamine, and isopropylamine; and the cycloalkyl monoamines such as cyclopentylamine and cyclohexylamine.

Examples of triazone compounds which may be employed in conjunction with the tris(N-methylol-carbamoylethyl) amine in the padding bath are dimethylol ethyl triazone, i.e., 1,3 dimethylol-5-ethyl-tetrahydro-S-triazone-Z; dimethylol methyl triazone, i.e., 1,3 dimethylol-S-methyltetrahydro-S-triazone-Z or hydroxyethyl dimethylol triazone, i.e., 1,3 dimethylol-5-hydroxyethyl-tetrahydro-S- triazone-2, preferably dimethylol ethyl triazone.

These triazone compounds, prepared as briefly described above, have a beneficial effect on the tensile strength of the fabric. This beneficial effect can be observed with the use of as little as 5 mol percent of the triazone in conjunction with 95 mol percent of the tris(N-methylol carbamoylethyl)arnine. Excellent results have also been obtained with as much as 50 mol percent of triazone mixed with 50 mol percent of a tris(N-methylol carbamoylethyl) amine.

The treating solution comprising a substantially aqueous solution of tris(N-methylol carbamoylethyl)amine, catalyst and a triazone, prepared as described above is padded onto the cloth by passing through efficient squeeze rolls to give a wet pickup of approximately 70 to 80 percent. The impregnated fabric is dried atfrom 100 to 150 C., followed by curing for from 1 to 5 minutes at 150 to 180 C., or the drying and curing may be combined into a single operation, using an appropriate time and temperature. The curing step may be followed by an alkaline afterwash in warm detergent solution and dried.

The padding baths may also contain additional materials such as softeners, lubricants, stiffening agents, water repellents, mildew inhibitors, wetting agents or other compounds as desired. The only precaution which need be exercised in the selection of such supplementary materials is that they be compatible with the catalyst and that they are not, in themselves, chlorine retentive.

In order to" further describe the invention, but without intent of limitations, the following illustrative embodiments are set forth.

EXAMPLE I Preparation of tris(2-carbam0ylethyl)amine EXAMPLES II-V Preparation of tris(N-m'ethylol-carbamoylelhyl)amine Four tris(N-methylol-carbamoylethyl) amine compositions were prepared having the following constituents:

Example No II III IV V Tris(carbamoylethyl)amine (g) 28. 2 28. 2 28. 2 28. 2' Formaldehyde (37% solution) (g.) 32. 7 45. 9 53. 6 61. 2 Water (g.). 38.5 25.3 17.6 10.0 pH. 8 8 8 8 Ratio, Formaldehyde:Tris-amine 3.2:1 4.5:1 5.25:1 6. :1

In the preparation of the tris(N-methylol-carbamoylethyl) amines shown in Table I above, 28.8 grams of tris(carbamoylethyl) amine were dissolved in water. this solution, a 37 percent neutralized formaldehyde solution was added and the pH adjusted to approximately 8. The resulting solution containing approximately 33 percent solids concentration was stirred for approximately 24 hours 'at room temperature.

Example II above, while illustrative of the prior art,

is included for purposes of comparison only and is not.

to be considered as a specific embodiment of this invention.

EXAMPLE VI The tris(N-methylol-carbamoylethyl)amine solution prepared in Example II above containing 3.2 mols of formaldehyde per mol of tris-amine was diluted with sufficient water to give a 10 percent solids concentration.

About 1.5 percent by weight of hydrated magnesium chloride was added as catalyst along with sutficient concentrated hydrochloric acid to adjust the pH of the solution to about 3.5. A sample of cotton broadcloth was.

treated with the padding bath solution to give av 70 to percent wet pickup. The wet fabric was driedv at a temperature of C. and then cured at C. for 3 minutes. The curing. step was. followed by an afterwash in Warm water in the presence of a non-ionic detergent, then dried. The finished fabric possesses a crease-recovery angle of 243 (warp+fill). When tested by the AATCC method of determining chlorine resistance of textiles, the cloth treated by this example shows a tensile strength loss of from 25 to 35%, or higher.

Example VI, while illustrative of the prior art, is included for purposes of comparison only and is not to be construed as a specific embodiment of this invention.

EXAMPLE VII The tris(N-methylol-carbarnoylethyl)amine solution prepared in Example III above containing 4.5 mols of formaldehyde per mol of tris-amine was diluted with sufficient water to give a percent solids concentration. About 1.5 percent by weight of hydrated magnesium chloride was added as catalyst along with a suffiicent amount of concentrated hydrochloric acid to adjust the pH of the solution to about 3.5. The treated solution was padded onto a sample of cotton broadcloth to give a 7080 percent wet pickup. The wet fabric was dried, cured, and washed in the presence of a non-ionic detergent. The finished fabric possesses a crease-recovery angle of 270 (warp-Hill). The chlorine resistance test shows a tensile strength loss of less than 20%.

EXAMPLE VIII(a) Tris(N-methylol-carbamoylethyl)amine prepared in Example IV above containing 5.25 mols of formaldehyde per mol of tris-amine was diluted with sufficient water to give a 7 percent solids concentration. About 1.0 percent by weight of magnesium chloride was added as a catalyst and the pH of the solution was adjusted to about 3.5 with concentrated hydrochloric acid. A sample of cotton broadcloth was treated with this padding solution to give a 70-80 percent wet pickup. The fabric was then dried, cured, and washed in the presence of a non-ionic detergent. The finished fabric was shrink-resistant and possessed a crease recovery angle of approximately 265 (warp-i-fill). The chlorine resistance test shows a tensile strength loss of less than 20%.

EXAMPLE VIII(b) Example VIII(a) was repeated, except that a viscose challis fabric was used in place of the cotton broadcloth. Equally excellent results were obtained.

EXAMPLE IX Tris(N-methylol-carbamoylethyl)amine prepared in Example V above containing 6 mols of formaldehyde per mol of tris-amine was diluted with sufiicient water to give a 10 percent solids concentration. About 1.5 percent by weight of magnesium chloride was added as a catalyst and the pH of the solution was adjusted to 3.5 with concentrated hydrochloric acid. A sample of cotton broadcloth was treated with this padding solution to give a 70-80 percent Wet pickup. The fabric was then dried, cured, and washed in the presence of a non-ionic detergent. The finished fabric possesses a crease-recovery angle of 284 (warp+fill), and when tested for chlorine resistance, the tensile strength loss is less than 15%. 7

EXAMPLE X (a) The tris(N-methylol-carbarnoylethyl)amine solution prepared in Example V above having 6.0 mols of formaldehyde per mol of tris-amine was diluted with sufficient water to give a 10 percent solids concentration. To this solution 3.0 percent by weight dimethylol ethyl triazone and 1.75 percent by weight of magnesium chloride was added. The pH of this solution was adjusted to 3.5 with concentrated hydrochloric acid. The treated solution was padded onto a sample of cotton broadcloth to give a 70-80 percent wet pickup. The wet fabric was dried at a temperature of 100 C. and then cured at 160 C. for 3 minutes. The curing step was followed by'an afterwash in warm water containing a non-ionic detergent, then dried. The finished fabric was shrink resistant, and had an initial crease recovery of approximately 280 (warp-f-fill). When checked for chlorine resistance, the strength loss was found to be less than 10%.

6 EXAMPLE X(b) Example X(a) was repeated, but the cotton broadcloth was replaced with an oxford shirting fabric woven from an intimate blend containing 50% cotton plus 50% of high-wet-modulus type regenerated cellulose fiber. Equally satisfactory results were obtained.

The fabrics were tested by the following methods: the crease-recovery values are total for warp plus fill, using AATCC Tentative Test Method 66-1959t; chlorine resistance performed by AATCC Tentative Test Method 92-1958t; and wash-wear performed by AATCC Tentative Test Method 88-19601 using Test 411 (spin-line dried) and using low angle illumination and three dimensional standards.

Table II is a comparison of the physical properties of fabrics which have been treated with tris(N-methylolcarbamoylethyl)amine solutions described in Examples VI, VII and IX initially and after five AATCC washes.

Quite surprisingly it has been found that fabrics treated with a product prepared from the reaction of from 4.5 to 6.0 mols of formaldehyde per mol of tris amine compound exhibits a greater resistance to chlorine retention. Likewise, it has been found that fabric treated with, for instance, the composition of Example VI, shows approximately a 25-30% tensile strength loss, whereas fabric treated with the compositions of our invention (Examples VII through X) show tensile strength losses of less than 20% when checked for chlorine resistance. The 20 percent tensile strength loss is generally considered the line of demarcation between those textile finishes which are considered chlorine resistant and those which are not considered chlorine resistant. A finish which causes more than a 20 percent loss in tensile strength due to chlorine retention is usually not considered acceptable for those types of textiles which are usually subject to periodic bleaching with hypochlorite. As can be seen from Example IX, the chlorine resistance is so good that the tensile strength loss is less than 15 percent. Further improvement in chlorine resistance is generally not required and the use of more than 6 mols of formaldehyde per mol of tris amine does not appreciably alter the resulting product.

Likewise, textile materials treated with tris(N-methy1olcarbamoylethyl)amines in the presence of a catalyst show high levels of crease resistance and wash-wear properties.

Even more significant when the tris(N-methylol-carbamoylethyl)amines are incorporated in a padding bath in the presence of a catalyst and a triazone, the tensile strength loss of textile materials thus treated is further reduced. Although an improvement in textile strength is obtained, the other properties of the treated cloth remain essentially the same as are normally obtained with tris(N-methylol-carbamoylethyl)amine alone.

The finish thus produced by tris (N-methylol-carbamoylethyl)amine having 4 or more mols of formaldehyde per mol of tris amine is far superior in resistance to damage 7 due to retained ohloride after 5 AATCC washes than the produced product by the reaction of 1 to 3 mols of formaldehyde per mol of tris amine. Furthermore, the finishes are resistant to discoloration due to heat and are durable through several launderings.

While there is disclosed above but a limited number of embodiments for the invention herein presented it is possible to produce still other embodiments without depart ing from the inventive concepts herein disclosed and it is desired therefore that only such limitations be imposed on the appended claims as are herein stated.

What is claimed is:

1. A process-for preparing novel compositions. of matter which comprises reacting 1 mole of tris(carbamoyl'- ethyl) amine with at least 4 mols of formaldehyde in a solvent at an alkaline pH until equilibrium is reached.

2. A process for preparing novel compositions of matter which comprises reacting '1 mol of tris(carbamoylethyl)amine with at least 4 mols of formaldehyde in an aqueous solventat an alkaline pH until equilibrium is reached.

3-. A process for preparing novel compositions of matter which comprises reacting 1' mol of tris(carbamoylethyl)amine with at least 4 mols of formaldehyde in an aqueous solvent at a pH of 7 to. 9 until equilibrium is reached.

4. A novel textile finishing composition comprising a tris(N-rnethylol-carban1oylethyl-)-amineobtained by re-' pH until equilibrium is reached, and an acid acting catalyst.

5. A novel textile finishing composition comprising a.

tris(N-methylol-carbamoylethyl)amine obtained by reacting 1' mol of a tris(carbamoylethyl') amine with at least 4 mols of formaldehyde in water at an alkaline pH untilequilibrium is reached, and an acid acting catalyst.

6. A novel textile finishing composition comprising a tris(N-methylol-carbamoylethyl)amine obtained by reacting 1 mol of a tris(carbamoylethyl')'amine with about 4.5 to 6.0 mols of formaldehyde in an aqueous solvent at a pH of 7 to 9 until equilibrium is reached, and a catalyst selected from the group consisting of maleic acid, tartaric acid, citric acid, zinc chloride, zinc nitrate and magnesium chloride.

7. The product having the formula:

O CHscHz Iu z Hh wherein n is an integer of 1 or 2 and the sum of all ns is equal to 4 to 6 inclusive.

8. A novel textile finishing composition comprising a tris(N-rnethylol-carbamoylethyl)amine obtained by reacting 1 mol of a tris(ca-rbamoylethyl)amine with at least 4 mols of formaldehyde in a solvent at a pH of 7 to 9 until equilibrium is reached, a 1,3-dimethy1ol-5 substituted triazone, and a catalyst selected from the group consisting of maleic acid, tartaric acid, citric acid, zinc chloride, zinc nitrate and magnesium chloride,

9. A novel textile finishing composition comprising a tris(N-methylol-carbamoylethyl) amine obtained by reacting 1 mol of a tris(carbamoylethyl)amine with at least 4 mols of formaldehyde in a solvent at a pH of 7 to 9 until equilibrium is: reached, a 1,3-dimethylol-5 substituted triazone, and magnesium chloride catalyst.

10. A novel textile finishing composition comprising a tris(N-methylol-carbamoylethyl)amine obtained by reacting 1' mol of a tris(carbamoylethyl)amine with at least 4 mols of formaldehyde in an aqueous solvent at a pH of 7- to 9 until equilibrium is reached, and 1,3-dirnethylo-l-5 ethyl triazone. and magnesium chloride catalyst.

11. The process of treating textile material with the composition of claim 4 to obtain improved properties which comprises the steps of impregnating the textile material with a solution containing between 2 and 25 weight percent of said composition, drying and curing the treated material, and thereafter washing the treated material to remove the excess treating composition.

12. The process of treating textile material with the composition of claim 5 to obtain improved properties which comprises the steps of impregnating said textile material with an aqueous solution containing from 2 to 25 weight percent of said composition, drying and curing the treated material, and thereafter washing the treated material to remove the excess treating composition.

13. The process of treating textile material with the composition of claim 6 to obtain improved properties which comprises the steps of impregnating the textile material with an aqueous solution containing from 2 to 25 weight percent of said composition, drying and curing the treated material, and thereafter washing the treated material to remove the excess treating composition.

14. The process of treating textile material with the composition of claim 8 to obtain improved properties which comprises the steps of impregnating the textile material with an aqueous solution containing from 2 to 25 weight percent of said composition, drying and curing the treated material, and thereafter washing the treated material to remove the excess treating composition.

15. The process of treating textile material with the composition of claim 4 to obtain improved properties which comprises the steps of impregnating the textile material with a solution containing between 2 and 25 weight percent of said composition, drying the Wetted material at a temperature of from to C. and curing the dried material for at least 1 minute at a temperature of from 150 C. to C., and thereafter washing the treated composition. 7

16. The process of treating textile material with the composition of claim 4 to obtain improved properties which comprises the steps of impregnating the textile material with a solution containing between 2 and 25 weight percent of said composition, drying and curing the treated material.

17. The process of treating textile material with the composition of claim 8 to obtain improved properties which comprises the steps of impregnating the textile material with an aqueous solution containing from 2 to 25 weight percent of said composition, drying and thereafter curing the treated material.

References Cited by the Examiner UNITED STATES PATENTS 2,663,733 12/53 Subluskey 117139.4 XR 2,846,337 8/58 Cooke et al 117139.4 2,901,463 2/59 Hurwitz 117139.4 XR 3,002,859 10/61 Hurwitz 117139.4 XR

WILLIAM D. MARTIN, Primary Examiner.

RICHARD D. NEVIUS, Examiner. 

4. A NOVEL TEXTILE FINISHING COMRPOSITION COMPRISING A TRIS (N-METHYLOL-CARBAMOYLETHYL) AMINE OBTAINED BY REACTING 1 MOL OF A TRIS (CARBAMOYLETHYL) AMINE WITH AT LEAST 4 MOLS OF FORMALDEHYDE IN A SOLVENT AT AN ALKALINE PH UNTIL EQUILIBRIUM IS REACHED, AND AN ACID ACTING CATALYST.
 11. THE PROCESS OF TREATING TEXTILE MATERIAL WITH THE COMPOSITION OF CLAIM 4 TO OBTAIN IMPROVED PROPERTIES WHICH COMPRISES THE STEPS OF IMPREGNATING THE TEXTILE MATERIAL WITH A SOLUTIN CONTAINING BETWEEN 2 AND 25 WEIGHT PERCENT OF SAID COMPOSITION, DRYING AND CURING THE TREATED MATERIAL, AND THEREAFTER WASHING THE TREATED MATERIAL TO REMOVE THE EXCES TREATING COMPOSITION. 